Indophenol azine compounds



Patented duly l9 1%32 rarenaiezi ELLUTH, or are rue, or n ELI], Y, ASSIG-NOR TO GENERAL ANILINE VORKS,

INDOPEZELIOL AZZNE COT/[POUNDS No Drawing. Application filed December 2 3, 1930, Serial No. EMA-12, and in Germany February 14, 1927.

the probable formula wherein A and B signify hydrogen or methyl or jointly stand for the grouping 3ll CH CH CI L 7' CH CH stand for by rogen or ing -CH=Cl1- C or i 2 CH CH CH G stands for hydrogen or chlorine, B represents hydrogen or niethyl and :0 means oxygen or sulfur.

In accordance with the present invention the new compounds are produced by joint oxidation of a compound of the general formula:

wherein A, B, D, E, sun :0 above mentioned A, B, D,

a para-aminophenol or by con compound of said type with I form an indophenol'a -d if desired with a reducing agent, such L s sulfide, alkali metal bisuliite hydrosuliide to form the leucocompound. Amongst processes which lead to my new 1 dophenols, I mention as particularly useful the joint oxidation of these said compounds with a para-aminophenol in aqueous mineral acid solution by means of an alkali metal bichromate, though in certain cases condensation with a quinone-halogen-imid or a paranitrosophenolmight be preferred. Substantially identical indophenolic compounds are, however, produced when using the qualified materials.

dy new compounds are generally lightgreyish crystalline powders, soluble in warm water, alcohol and sulfuric acid, sparingly soluble in saltsolutions. They form colorless solutions with aqueous alkalies, in which the leuco-indophenols are easily oxidized as already in contact with atmospheric oxygen to the corresponding dark colored indophenols. They produce in the 'polysulfide melt Va uable sulfur dyestuffs.

The following examples will illustrate my invention without restricting it thereto EwampZe 1.9,8 kgs. of phenmorpholine, prepared according to the process described in Ber. d. Deutschen Chem. Ges. Vol. 55, page 3821, and 8,6 kgs. of para-aminophenol are dissolved in 500 liters of waterv by the additionof 250 liters of hydrochloric acid of 19,9 B.; the solution is well cooled with ice and a solution of 14,5 lrgs. of sodium. bichromate is allowed to run in. Immediately after the oxidation is complete, 250 liters of an aqueous caustic soda solution of 30% strength is added and the indophenol formed is reduced by means of sodium sulfide until the deep red coloration is converted into the light yellow coloration of the leuc'o-indophenol. It is then rendered distinctly acid to congo with diluted hydrochloric acid, heated to 60 C. and after the addition of sodium chloride allowed to cool. The leuco-indophenol of the probable formula I separates as a pale yellowish sandy powder.

H: EZ-methyl-phenmorpholine, prepared according to the process described in Ber. d.

Deutschen Chem. Ges. vol. 30, page 1635, having the probable formula 1,2-dimethylphenmorpholine of the probable formula and alpha-beta-naphthodihydroisooxazine, prepared according to the process described in Journ. Chem. Soc. London, vol. 121, page 6 17 of the probable formula Example 2.20,1 kgs. of phenmorpholine are dissolved as in Example 1 and oxidized N with an aqueous suspension of 37 kgs. of the sulfate of 2.6-dichloro-para-aminophenol in an analogous manner as described in Example 1, reduced and separated. The behaviour of the leuco-indophenol of the probable formula 01 I HOQNH- (fH2 01 N /CH2 towards aqueous caustic soda solution is analogous to that of Example 1. In an analogous manner from hexahydro-phenoxazine the product of the probable formula is prepared.

Example 3.-10,4 kgs. of 2.3-dihydrobenzene-para-thiazine and 8,6 kgs. of paraaminophenol are condensed as described in Example 1.

The new indophenol of the probable formula Flo-ONE cm N Ha 1'1 possesses similar properties as the product described in Example 1.

In analogous manner a compound of the probable formula is obtained from alpha-beta-naphthddihydroisothiazine.

This is a continuation in part of my copending application Serial No. 252,680, filed February 7, 1928.

I claim:-

1. As new products compounds of the probwherein A and B signify hydrogen or methyl or jointly stand for the grouping CH2 CH2 CH2' GH2CH2 CH2 OI CH2 CH2 CH2 CH2' GH2' D and E stand for hydrogen or jointly for the grouping CH=CHCH CH or CH CH CH CH Gr stands for hydrogen or chlorine, R represents hydrogen or methyl andwmeans oxygen orrsulfur, being generally light-greyish crystalline powders, soluble in warm water, alcohol and sulfuric acid, sparingly soluble in salt solutions, forming colorless solutions with aqueous alkalies,

in which the leuco-indophenol is easily oxidized to the corresponding dark colored indophenol and producing in the polysulfide melt very valuable sulfur dyestuffs.

2. As a new product the compound of the formula:

N OHz being a light greyish crystalline powder, soluble in hot water, alcohol and mineral acids, sparingly soluble in salt solutions, forming colorless solutions with aqueous alkalies, in which the leuco-indophenol is easily oxidized to the corresponding dark colored indophenol, producing in the polysulfide melt a very valuable sulfur dyestufl.

3. As a new product the compound of the ,7

formula N CH:

being a light greyish crystalline powder, soluble in hot water, alcohol and mineral acids, sparingly soluble in salt solutions, forming colorless solutions with aqueous alkalies in which the leuco-indophenol is easily oxidized to the corresponding dark colored indophenol, producing in the polysulfide melt a very valuable sulfur dyestufi.

In testimony whereof, I aflix my signature.

FRIEDRICH MUTH. 

